Functional Acetal Methacrylates: IV. Electrophophilic Addition of Triazoles to Vinyloxyalkyl Methacrylates

Reactions of vinyloxyalkyl methacrylates with triazoles (1,2,4-triazole, 1,2,3-benzotriazole, 5-methyl-1,2,3-benzotriazole) under electrophilic conditions (50°C, 1-2 h, 1 wt% CF₃COOH) occur chemoselectively and afford in quantitative yield polyfunctional methacrylates with triazole and benzotriazole yields.     

Reactions of elemental phosphorus and phosphine with electrophiles in superbasic systems: XVIII. Phosphorylation of 1-(chloromethyl)naphthalene with the elemental phosphorus

1-Chloromethylnaphthalene reacts with white and red phosphorus, and also with the “activated red phosphorus,” the complex organophosphorus polymer of unknown structure obtained by irradiation of a solution of white phosphorus in benzene by the ⁶⁰Co source, in a system including KOH water solution, dioxane or benzene, and a phase transfer catalyst (22–98°C, argon), to form bis(1-naphthylmethyl)-and tris-(1-naphthylmethyl)phosphine oxides, and also (1-naphthylmethyl)phosphonous-and bis(1-naphthylmethyl)-phosphinic acids. The yield and the ratio of the reaction products depend on reaction conditions as well as on the nature of phosphorylating agent. It is shown that the reactivity of the “activated red phosphorus” is not worse than that of the white phosphorus and significantly exceeds the reactivity of the usual technical red phosphorus.     

Formation and Properties of Hydrogenation Catalysts Based on Palladium Complexes with Primary Phosphines

The formation and catalytic properties of hydrogenation catalysts based on palladium(II) complexes with primary phosphines were studied. With the use of IR and UV spectroscopy, XRD analysis and GLC, it was found that the interaction of bis(acetylacetonato)palladium(II) or palladium(II) acetate with primary phosphines in an inert atmosphere resulted in the formation of polynuclear palladium complex associates mainly containing μ³-PR and a coordinated phosphine. Polynuclear palladium complexes and the palladium phosphide Pd₆P, which is formed from these complexes in an atmosphere of hydrogen, serve as supports for Pd(0) clusters. The effects of the ratio between initial components and the nature of the acido ligand at the palladium atom on the optimum conditions of catalyst formation were considered.__________Translated from Kinetika i Kataliz, Vol. 46, No. 4, 2005, pp. 609–614.Original Russian Text Copyright © 2005 by Belykh, Goremyka, Gusarova, Sukhov, Shmidt.     

Molecular dynamics simulation of thermomechanical properties of montmorillonite crystal. 3. montmorillonite crystals with PEO oligomer intercalates

We present the results of molecular dynamics (MD) simulation of the structure and thermomechanical behavior of Wyoming-type Na+-montmorillonite (MMT) with poly(ethylene oxide) (PEO) oligomer intercalates. Periodic boundary conditions in all three directions and simulation cells containing two MMT lamellae [Si248Al8][Al112Mg16]O640[OH]128 oriented parallel to the XY-plane were used. The interlamellar space, or gallery, between neighboring MMT lamellae was populated by 24 Na+ counterions and PEO macromolecules of different lengths, ranging from 2 up to 240 repeat units. We considered three different loadings of PEO within the gallery: 80, 160, and 240 repeat units, corresponding to 13, 23, and 31 wt % PEO based on total mass of the nanocomposite, respectively. In the cases of 13 and 23 wt %, the polymer chains formed one or two well-defined amorphous layers with interlayer distances of 1.35 and 1.8 nm, respectively. We have observed also formation of a wider monolayer gallery with interlayer distances of 1.6 nm. Three-layer PEO films formed in the case of 31 wt % loading. The thermal properties were analyzed over the range 300-400 K, and the isothermal linear compressibility, transversal moduli, and shear moduli were calculated at 300 K. These properties are compared with the results of our simulation of thermal and mechanical properties of MMT crystal with galleries filled by one or two water layers as well as with those of an isolated clay nanoplate.     

Reaction of imidazole series aldeydes with bis[2-(2-pyridyl)ethyl]-phosphine chalcogenides: Synthesis of polyfunctional heterocyclic systems

The nucleophilic addition of bis[2-(2-pyridyl)ethyl]phosphine sulfide and bis[2-(2-pyridyl)-ethyl]phosphine selenide to 2-formyl-1-organylimidazoles and benzimidazoles occurs efficiently without catalysis at room temperature to give functionalized heterocyclic compounds containing imidazole, benzimidazole, and pyridine rings and also chalcogenophosphoryl and hydroxyl groups. Dedicated to Professor A. Pozharskii on his 70th jubilee Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1669–1675, November, 2008.     

Straightforward Solvent‐Free Synthesis of Tertiary Phosphine Chalcogenides from Secondary Phosphines,Electron‐Rich Alkenes,and Elemental Sulfur or Selenium

A series of tertiary phosphine sulfides and selenides have been synthesized in excellent yields (88‐99%) via a three‐component reaction between secondary phosphines, electron‐rich alkenes (styrene, vinyl chalcogenides), and elemental sulfur or selenium, proceeding under solvent‐free conditions (80‐82°C, 4–44 h). The interaction occurs via initial oxidation of secondary phosphines with elemental sulfur or selenium followed by noncatalyzed anti‐Markovnikov addition of the generated R₂P(E)H (E = S, Se) species to alkenes to afford the corresponding adducts with high chemo‐ and regioselectivity.     

Proton-transfer polyaddition reactions in syntheses of linear,branched, and functionalized poly(p-divinyl aromatics). I. Synthesis,kinetics, and mechanism of formation of linear unsaturated poly[bis(p-vinylphenyl) ether]

A peculiar step-growth (cationic) polymerization of bis(p-vinylphenyl) ether (BVPE) in nonpolar or slightly polar aromatic solvents in the temperature range from 70 to 150°C in the presence of 2.5–5.0 mmol/L of p-toluenesulfonic acid has been studied. Optimum polymerization conditions were found. New linear unsaturated polymers of BVPE with terminal vinyl groups and weight-average molecular weight from 1500 to 10,000 were obtained. The structure and the formation mechanism of these oligomers and polymers were established, and the accompanying side reactions were considered. The rate constants were measured for eight temperatures, and the activation energy was found to be −42 kJ/mol. The optimum polymerization temperature was about 80°C. © 1996 John Wiley & Sons, Inc.     

Tris(2-phenylethyl)phosphine oxide from red phosphorus and styrene

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1705–1706, July, 1989.     

Chemoselective Vinylation of the Quinine Hydroxy Group with the System Electron-Deficient Acetylene/Diphenylphosphine Oxide: an Alternative to SNHAr Reaction

Russian Journal of Organic Chemistry - Three-component SNHAr reaction of quinine, diphenylphosphine oxide, and furoylacetylene chemoselectively afforded the corresponding quinine vinyl ether and 2:...     

Catalyst-free regio- and chemoselective addition of secondary phosphine oxides to isoquinolines

Russian Chemical Bulletin - Isoquinolines react with secondary phosphine oxides without catalyst (70–75 °C, 10–15 h, without solvent or in MeCN) to chemo- and regioselectively form...